Processing aids, masterbatches, thermoplastic resin compositions and molded articles, and methods for producing the same.

Abstract

To provide a processing aid and a master batch which can improve processibility of a thermoplastic resin, a thermoplastic resin composition and a molded body using them, and a method for manufacturing them.SOLUTION: A processing aid contains a lubricant (A) and a resin (B), wherein the resin (B) includes a structural unit represented by formula 1: -X-(CR1R2)n-Y-(CR3R4)m-Z-.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This disclosure relates to processing aids, masterbatches, thermoplastic resin compositions and molded articles, and methods for producing the same. [Background technology]

[0002] In processing melt-processable thermoplastic resins, high extrusion speeds are necessary to improve productivity and reduce costs. However, melt-processable thermoplastic resin compositions always have a critical shear rate, and exceeding this rate results in a surface roughening condition called melt fracture, making it impossible to obtain good molded products.

[0003] As a method to improve the processability of thermoplastic resins, for example, Patent Document 1 proposes a method containing ethylene vinyl alcohol, and Patent Document 2 proposes a method containing a surfactant and polyethylene glycol. However, the effect was not sufficient. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 1-215840 [Patent Document 2] U.S. Patent Application Publication No. 2023 / 0031000 [Overview of the project] [Problems that the invention aims to solve]

[0005] This disclosure aims to provide processing aids and masterbatches that can improve the processability of thermoplastic resins, as well as thermoplastic resin compositions and molded articles using these. This disclosure also aims to provide methods for manufacturing these. [Means for solving the problem]

[0006] The present disclosure (1) contains a lubricant (A) and a resin (B), where the resin (B) is a processing aid containing a structural unit represented by the following formula 1. -X-(CR ,

[0009] , 4 , , ,

[0007] , , , ,

[0008] , , R 2 ) n -Y-(CR 3 R 4 ) m -Z- (Formula 1) (In Formula 1, X is a divalent group which may have a single bond or a functional group, Y and Z are each independently a group composed of at least one selected from the group consisting of a single bond, -O-, -C(=O)-, -C(=O)O-, -OC(=O)O-, -C(=NR’)-, -C(=NR’)O-, -OC(=NR’)O-, -S-, -S(=O)-, -S(=O)O-, -OS(=O)O-, -S(=O)2-, -S(=O)2O-, -OS(=O)2O-, -P(=O)-, -P(=O)O-, -OP(=O)O-, -P(=O)2-, -P(=O)2O-, -OP(=O)2O-, -NR’-, and -C(OR’)R’- (wherein R’ is independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms in each occurrence).), R 1 , R 2 , R 3 and R[[ID=二十九]] 4 are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, n and m are each independently an integer from 0 to 10, at least one of X, Y and Z is -C(=O)-, -C(=O)O-, -OC(=O)O- or -C(OR’)R’-.)

[0007] The present disclosure (2) is the processing aid described in the present disclosure (1) that substantially does not contain fluorine.

[0008] The present disclosure (3) is the processing aid described in the present disclosure (1) or (2) wherein the lubricant (A) is at least one selected from the group consisting of waxes, alcohols and surfactants.

[0009] Disclosure (4) is a processing aid according to any one of Disclosures (1) to (3), wherein the lubricant (A) is at least one selected from the group consisting of sugar-type surfactants, metal soaps, and polyethylene waxes.

[0010] This disclosure (5) states that in formula 1, X is X 1 and X 2 A divalent group consisting of at least one selected from the group comprising, X 1 This is a group composed of at least one selected from the group consisting of -C(=O)-, -C(=NR')-, -S(=O)2-, -NR'-, -CR'R'-, and -C(OR')R'- (wherein R' is independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms in each occurrence). X 2 The processing aid is an aromatic hydrocarbon group having 1 to 12 carbon atoms, which may have substituents, as described in any of (1) to (4) of this disclosure.

[0011] The present disclosure (6) is a processing aid according to the present disclosure (5), wherein X in formula 1 is a divalent group comprising at least one selected from the group consisting of -C(=O)-, -CR'R'-, and -C(OR')R'- (wherein R' is independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms in each occurrence).

[0012] Disclosure (7) is a processing aid according to any one of Disclosures (1) to (6), wherein Y and Z in Formula 1 are each independently composed of at least one selected from the group consisting of a single bond, -O-, -C(=O)-, -C(=O)O-, -C(=NR')-, -C(=NR')O-, -S-, -S(=O)2-, -S(=O)2O-, -NR'-, and -C(OR')R'- (wherein R' is independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms in each occurrence).

[0013] The present disclosure (8) is a processing aid according to the present disclosure (7), wherein Y and Z in formula 1 are each independently composed of at least one group selected from the group consisting of a single bond, -O-, -C(=O)-, and -C(=O)O-.

[0014] Disclosure (9) is a processing aid according to any of Disclosures (1) to (8), wherein the melting point of the resin (B) is 65°C or higher.

[0015] Disclosure (10) is a processing aid according to any one of Disclosures (1) to (9), wherein the resin (B) is at least one selected from the group consisting of polylactic acid, polybutylene succinate, ethylene-vinyl alcohol copolymer, and polybutylene succinate adipate.

[0016] The present disclosure (11) is a processing aid according to any one of the present disclosures (1) to (10), wherein the lubricant (A) is at least one selected from the group consisting of polysorbate, zinc stearate, magnesium 12-hydroxystearate, and polyethylene wax, and the resin (B) is at least one selected from the group consisting of polylactic acid, polybutylene succinate, and ethylene-vinyl alcohol copolymer.

[0017] Disclosure (12) is a masterbatch comprising a processing aid described in any of Disclosures (1) to (11) and a thermoplastic resin (C).

[0018] This disclosure (13) is the masterbatch according to this disclosure (12), wherein the thermoplastic resin (C) is a polyolefin resin.

[0019] (14) The present disclosure is a masterbatch according to (12) or (13), wherein the thermoplastic resin (C) is at least one selected from the group consisting of metallocene-catalyzed linear low-density polyethylene and Ziegler-Natta-catalyzed linear low-density polyethylene, and the mass ratio of the thermoplastic resin (C) to the processing aid (thermoplastic resin (C): processing aid) is 92:8 to 70:30.

[0020] Disclosure (15) is a thermoplastic resin composition comprising a processing aid described in any of Disclosures (1) to (11), and / or a masterbatch described in any of Disclosures (12) to (14), and a thermoplastic resin (D).

[0021] The present disclosure (16) is a thermoplastic resin composition according to the present disclosure (15), wherein the thermoplastic resin (D) is a polyolefin resin.

[0022] The present disclosure (17) is a thermoplastic resin composition according to the present disclosure (15) or (16), wherein the thermoplastic resin (D) is at least one selected from the group consisting of metallocene-catalyzed linear low-density polyethylene and Ziegler-Natta-catalyzed linear low-density polyethylene, and the content of the processing aid is 0.02 to 3% by mass.

[0023] Disclosure (18) is a molded article using a thermoplastic resin composition described in any of Disclosures (15) to (17).

[0024] The present disclosure (19) is a molded article according to the present disclosure (18), which is in the form of a tube, a film, or a sheet.

[0025] This disclosure (20) is a method for producing a processing aid according to any of the disclosures (1) to (11), including a mixing step and a dispensing step.

[0026] This disclosure (21) is a method for producing a masterbatch according to any of this disclosure (12) to (14), including a mixing step and a dispensing step.

[0027] This disclosure (22) is a method for producing a thermoplastic resin composition according to any one of this disclosure (15) to (17), including a mixing step and an extrusion step.

[0028] The present disclosure (23) is a method for manufacturing a molded article according to the present disclosure (18) or (19), including a molding step. [Effects of the Invention]

[0029] According to this disclosure, the processability of thermoplastic resins can be improved. [Modes for carrying out the invention]

[0030] The following provides a detailed explanation of this disclosure.

[0031] <Processing aids> The processing aid of this disclosure comprises a lubricant (A) and a resin (B), The aforementioned resin (B) includes structural units represented by the following formula 1. -X-(CR 1 R 2 ) n -Y-(CR 3 R 4 ) m -Z- (Formula 1) (In formula 1, X is a divalent group which may have a single bond or a functional group, Y and Z are each independently composed of at least one group selected from the group consisting of a single bond, -O-, -C(=O)-, -C(=O)O-, -OC(=O)O-, -C(=NR')-, -C(=NR')O-, -OC(=NR')O-, -S-, -S(=O)-, -S(=O)O-, -OS(=O)O-, -S(=O)2-, -S(=O)2O-, -OS(=O)2O-, -P(=O)-, -P(=O)O-, -OP(=O)O-, -P(=O)2-, -P(=O)2O-, -OP(=O)2O-, -NR'-, and -C(OR')R'- (wherein R' is independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms in each occurrence). R 1 , R 2 , R 3 and R 4 Each of these is independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. n and m are independent integers between 0 and 10. At least one of X, Y, and Z is -C(=O)-, -C(=O)O-, -OC(=O)O-, or -C(OR')R'-.

[0032] The above lubricant (A) is an additive that reduces friction and improves slipperiness, and examples include waxes, alcohols, and surfactants. One of these can be used alone, or two or more can be used in combination. The above lubricant (A) is preferably at least one selected from the group consisting of waxes, alcohols, and surfactants, more preferably at least one selected from the group consisting of waxes and surfactants, and even more preferably a surfactant.

[0033] Examples of the above-mentioned waxes include pure hydrocarbon waxes such as liquid paraffin, natural paraffin, microwax, synthetic paraffin, polyethylene wax, and polyethylene / polypropylene wax; fatty acid waxes such as higher fatty acids and oxy fatty acids; fatty acid amide waxes such as fatty acid amides and bis-fatty acid amides; and fatty acid ester waxes such as lower alcohol esters of fatty acids, polyhydric alcohol esters of fatty acids such as glycerides, polyglycol esters of fatty acids, and aliphatic alcohol esters of fatty acids (ester waxes). Among these, pure hydrocarbon waxes and fatty acid ester waxes are preferred, with pure hydrocarbon waxes being more preferred. As for pure hydrocarbon waxes, polyethylene wax and polyethylene / polypropylene wax are preferred, with polyethylene wax being more preferred. As for fatty acid ester waxes, adipic acid esters and glycerin fatty acid esters are preferred. Examples of polyethylene waxes include general polymerization polyethylene wax, metallocene catalyst polyethylene wax, acid-modified polyethylene wax, oxidation-type (slightly oxidation, high acid value) polyethylene wax, and aromatic monomer-modified polyethylene wax. Examples of acid-modified polyethylene waxes include those copolymerized with vinyl carboxylic acids such as acrylic acid and methacrylic acid, examples of oxidation-type polyethylene waxes include those obtained by air oxidation or thermal decomposition of polyethylene, and examples of aromatic monomer-modified polyethylene waxes include those modified by graft polymerization of styrene monomer.

[0034] Examples of fatty acid ester waxes include phthalates, dimethyl succinates and diethyl succinates and related esters, glycerol monoacetate, glycerol diacetate, glycerol triacetate, glycerol monoacetate, citrate esters, adipic acid esters, stearic acid esters, and oleic acid esters. These may be used individually or in combination of two or more types.

[0035] Examples of adipate esters include diadipate esters. Specifically, these include dimethyl adipate, dibutyl adipate, bis[2-(2-methoxyethoxy)ethyl] adipate, bis(butyl diglycol) adipate, bis(methyl diglycol) adipate, benzyl[2-(2-methoxyethoxy)ethyl] adipate, di-n-butyl adipate, dioctyl adipate, methyl diglycol butyl diglycol adipate, benzyl methyl glycol adipate, benzyl butyl diglycol adipate, and diisononyl phthalate. These may be used individually or in combination of two or more. Among these, diisononyl phthalate and dioctyl adipate are preferred.

[0036] Examples of glycerin fatty acid esters include glycerin monostearate, glycerin monobehenate, glycerin mono-12-hydroxystearate, glycerin monooleate, glycerin monocaprylate, glycerin monocaprate, glycerin monolaurate, glycerin diacetomonolaurate, succinic acid fatty acid monoglyceride, citrate fatty acid monoglyceride, diacetyltartrate fatty acid monoglyceride, diglycerin laurate, diglycerin stearate, diglycerin oleate, and di Examples include glycerin monolaurate, diglycerin monomyristate, diglycerin monostearate, diglycerin monooleate, tetraglycerin stearate, decaglycerin laurate, decaglycerin stearate, decaglycerin oleate, polyglycerin polyricinolate, propylene glycol monolaurate, propylene glycol monopalmitate, propylene glycol monostearate, propylene glycol monooleate, and propylene glycol monobehenate. These may be present individually or in combination of two or more. Among these, glycerin diacetomonolaurate and decaglycerin stearate are preferred.

[0037] The acid value of the above waxes is preferably 40 mg KOH / g or less, more preferably 30 mg KOH / g or less, and even more preferably 20 mg KOH / g or less. The lower limit is not particularly limited and may be 0 mg KOH / g. Within the above range, the improvement effect on processability is better. The above acid value represents the number of milligrams of potassium hydroxide required to neutralize the free acid contained in 1 g of wax. The acid value of wax can be measured, for example, by a general neutralization titration method (JIS K 0070:1992).

[0038] The melting point of the above waxes is preferably 40°C or higher, more preferably 60°C or higher, even more preferably 80°C or higher, and also preferably 200°C or lower, more preferably 160°C or lower, and even more preferably 130°C or lower. Within this range, the effect of improving processability is better. In this specification, the melting point is the temperature corresponding to the maximum value in the heat of fusion curve when the temperature is increased at a rate of 10°C / min using a differential scanning calorimetry (DSC) device.

[0039] The melt viscosity of the above waxes at 140°C is preferably 20 mPa·s or more, more preferably 40 mPa·s or more, even more preferably 60 mPa·s or more, and also preferably 500 mPa·s or less, more preferably 400 mPa·s or less, and more preferably 350 mPa·s or less. Within the above range, the improvement effect on processability is better. The above melt viscosity was measured in accordance with ISO 11443, using a flow tester (manufactured by Shimadzu Corporation) and a 2φ-8L die. A 2g sample, preheated to 140°C for 5 minutes, was maintained at the above temperature under a load of 0.7MPa.

[0040] The alcohols mentioned above include fatty alcohols such as higher alcohols; and polyhydric alcohols such as polyglycols and polyglycerols. These may be one type or two or more types.

[0041] Examples of fatty alcohols include lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, and behenyl alcohol. These may be present individually or in combination of two or more types.

[0042] Examples of the above-mentioned surfactants include anionic surfactants such as metal soaps and ammonium salts; cationic surfactants such as alkylamine salts and quaternary ammonium salts; nonionic surfactants such as ester type, ether type, ester / ether type, and amide type; and amphoteric surfactants such as aminocarboxylate salts, alkyl betaines, and alkylimidazoline derivatives. Among these, anionic surfactants or nonionic surfactants are preferred. As anionic surfactants, metal soaps are preferred, specifically carboxylate salts, sulfate salts, sulfonates, and phosphate ester salts. As nonionic surfactants, ester / ether type surfactants are preferred, specifically sugar-type surfactants.

[0043] Examples of the above-mentioned metal soaps include fatty acid salts, polysulfonates, polycarboxylates, alkyl sulfates, alkylaryl sulfonates, alkylnaphthalene sulfonates, dialkyl sulfonates, dialkyl sulfosuccinates, alkyl phosphates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkylaryl ether sulfates, and polyoxyethylene alkyl phosphate sulfonates. Specifically, examples include sodium dodecylbenzenesulfonate, sodium lauryl sulfate, sodium polyoxyethylene lauryl ether sulfate, and polyoxyethylene nonylphenyl ether sulfate. These may be used individually or in combination of two or more.

[0044] The above-mentioned metal soap is preferably a compound represented by the following general formula (1). (R 5 COO) n1 M 1 (1) (In the above general formula (1), R 5 n1 is a hydrogen atom or an alkyl group having 1 to 21 carbon atoms, n1 is an integer in the range of 1 to 4, and M 1These are lithium, sodium, potassium, rubidium, cesium, boron, magnesium, aluminum, calcium, manganese, iron, cobalt, nickel, tin, antimony, copper, silver, zinc, molybdenum, vanadium, strontium, zirconium, barium, bismuth, lead, gold, platinum, or rare earth elements.

[0045] In the general formula (1) above, if n1 is an integer greater than or equal to 2, then multiple R 5 They may be the same or different from each other.

[0046] R 5 The alkyl group having 1 to 21 carbon atoms may be a linear alkyl group, a branched alkyl group, or may contain an alicyclic structure.

[0047] R 5 The alkyl groups with 1 to 21 carbon atoms are used in the production of fatty acid metal salts. 5 This corresponds to carboxylic acid residues obtained by removing the carboxyl group (COOH) from carboxylic acids with 1 to 22 carbon atoms represented by COOH. Examples of such carboxylic acid residues include acetic acid residues, propionic acid residues, butanoic acid residues, pentanoic acid residues, acrylic acid residues, methacrylic acid residues, octic acid residues (2-ethylhexanoic acid residues), neodecanoic acid residues, naphthenic acid residues, isononanoic acid residues, tung oil acid residues, tall oil fatty acid residues, coconut oil fatty acid residues, soybean oil fatty acid residues, linseed oil fatty acid residues, safflower oil fatty acid residues, dehydrated castor oil fatty acid residues, tuni oil fatty acid residues, lauric acid residues, myristic acid residues, palmitic acid residues, stearic acid residues, isostearic acid residues, oleic acid residues, and 12-hydroxystearic acid residues.

[0048] R 5 From the viewpoint of improving processability, the alkyl group having 1 to 21 carbon atoms is preferably an alkyl group having 12 to 21 carbon atoms, more preferably an alkyl group having 16 to 21 carbon atoms, and even more preferably a stearic acid residue or a 12-hydroxystearic acid residue.

[0049] M 1These are lithium, sodium, potassium, rubidium, cesium, boron, magnesium, aluminum, calcium, manganese, iron, cobalt, nickel, tin, antimony, copper, silver, zinc, molybdenum, vanadium, strontium, zirconium, barium, bismuth, lead, gold, or platinum.

[0050] n1 is M 1 This is a numerical value determined by the ionic charge of the metal atoms, for example, M 1 If it is boron, then n1 will be 3, and M 1 If n1 is cobalt, then n1 will be 2.

[0051] The above-mentioned metal soaps also include the form of metal salts of fatty acid borates. These metal salts of fatty acid borates are compounds represented by the following general formula (2). (R 6 COO-M 2 -O)3B (2) (In the above general formula (2), R 6 M is a hydrogen atom or an alkyl group having 1 to 21 carbon atoms. 2 These are boron, magnesium, aluminum, calcium, manganese, iron, cobalt, nickel, tin, antimony, copper, zinc, molybdenum, vanadium, strontium, zirconium, barium, bismuth, lead, gold, or platinum.

[0052] In the above general formula (2), R 6 The alkyl group having 1 to 21 carbon atoms is R in the general formula (1) above. 5 It is the same as an alkyl group having 1 to 21 carbon atoms. Similarly, in the above general formula (2), M 2 The metal is M of the general formula (1) above. 1 It is the same as the metal.

[0053] The above metal soaps may be used individually, or two or more metal soaps with different structures may be used together.

[0054] Specific examples of the above-mentioned metal soaps include metal salts of stearic acid and metal salts of hydroxystearate. Preferably, the above-mentioned metal soap is at least one selected from the group consisting of metal salts of stearic acid and metal salts of hydroxystearate, and more preferably at least one selected from the group consisting of zinc stearate, magnesium hydroxystearate, and calcium stearate. Furthermore, examples of metals constituting the above-mentioned metal salt include zinc, magnesium, and calcium, and it is preferable that at least one is selected from the group consisting of zinc, magnesium, and calcium, and more preferably that at least one is selected from the group consisting of zinc and magnesium. The above-mentioned metal soap can be manufactured by known methods, or a commercially available product may be used.

[0055] Examples of the above-mentioned ammonium salt-based anionic surfactants include fatty acid ammonium salts. For example, ammonium lauryl sulfate and polyoxyethylene lauryl ether ammonium sulfate are examples. The anionic surfactant may be one type or two or more types.

[0056] Examples of cationic surfactants include alkylamine salts and quaternary ammonium salts, specifically stearylamine acetate, trimethyl coconut ammonium chloride, trimethyl beef tallow ammonium chloride, dimethyl dioleyl ammonium chloride, methyl oleyl diethanol chloride, tetramethyl ammonium chloride, laurylpyridinium chloride, laurylpyridinium bromide, laurylpyridinium disulfate, cetyltrimethylammonium chloride, cetylpyridinium bromide, 4-alkyl mercaptopyridine, poly(vinylpyridine)-dodecyl bromide, and dodecylbenzyltriethylammonium chloride. The cationic surfactant may be one type or two or more types.

[0057] Examples of amphoteric surfactants include aminocarboxylate salts, alkyl betaine types, and alkylimidazoline derivatives, with lauryl amide propyl betaine being a specific example. The amphoteric surfactant may be one type or two or more types.

[0058] Examples of ether-type nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyalkylene derivatives, polyoxyethylene phenyl ethers, and alkylallyl ethers. Specifically, examples include polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, and polyoxyethylene octylphenyl ether. Examples of ester / ether-type nonionic surfactants include sugar-type surfactants. Specifically, these include sorbitan fatty acid esters, sorbitol, and polyoxyethylene sorbitan fatty acid esters. The nonionic surfactant may be one type or two or more types.

[0059] Examples of the sugar-type surfactants mentioned above include sucrose fatty acid esters, sorbitan acid esters, and polysorbates. Specific examples of the above sugar-type surfactants include sorbitol fatty acid esters such as sorbitol monolaurate, sorbitol monostearate, sorbitol monooleate, sorbitol trioleate, sorbitol tristearate, and sorbitol monoisostearate; sorbitan isostearate, sorbitan oleate, sorbitan caprylate, sorbitan dioleate, sorbitan distearate, sorbitan stearate, sorbitan sesquiisostearate, sorbitan sesquioleate, and sorbitan sesquioleate. Sorbitan fatty acid esters such as sorbitan dicaprylate, sorbitan sesquistearate, sorbitan triisostearate, sorbitan trioleate, sorbitan tristearate, sorbitan palmitate, sorbitan coconut fatty acid, sorbitan laurate, sorbitan olive fatty acid; sucrose acetate isobutyrate, sucrose octaacetate, sucrose oleate, sucrose distearate, sucrose dilaurate, sucrose stearate, tetraisostearate, tetra Sucrose hydroxystearate, sucrose tristearate, sucrose tribehenate, sucrose trilaurate, sucrose tetrastearate triacetate, sucrose palmitate, sucrose hexaerucate, sucrose hexapalmitate, sucrose pentaerucate, sucrose pentahydroxystearate, sucrose polyoleate, sucrose polystearate, sucrose polysoybean oil fatty acid, sucrose polypalm fatty acid, sucrose polybehenate, polylaurin Examples include sucrose fatty acid esters such as sucrose acid, polylinoleic acid sucrose, polycottonseed fatty acid sucrose, myristate acid sucrose, coconut fatty acid sucrose, laurate sucrose, ricinoleic acid sucrose, benzoate sucrose, distearate acetate sucrose, and stearate acetate sucrose; and alkyl glucosides such as coconut oil fatty acid glucoside, lauryl glucoside, decyl glucoside, myristyl glucoside, palmityl glucoside, stearyl glucoside, and coco glucoside. These may be used alone or in combination of two or more.

[0060] As the sugar-type surfactant, sorbitan esters containing a non-polar carboxylic acid (lipophilic group) bonded to a polar sorbitan group (hydrophilic group) by an ester bond are preferred. Also preferred are polyoxyethylene derivatives of sorbitan esters and a plurality of polyoxyethylene oligomers chemically substituted on the sorbitan group.

[0061] These polyoxyethylene derivatives of sorbitan esters are called polysorbates. Specifically, the polyoxyethylene derivative of sorbitan ester (also referred to as polysorbate) has the formula (I):

Chemical formula

[0062] Here, one of R 7 ~R 10 is a linear fatty acid moiety, and the other three of R 7 ~R 10 are each hydrogen. [[ID=​​​​​​​​​​​​​​​​​

[0063] Specific examples of polysorbates include polysorbate 20 (polyoxyethylene (20) sorbitan monolaurate), polysorbate 40 (polyoxyethylene (20) sorbitan monopalmitate), polysorbate 60 (polyoxyethylene (20) monostearate sorbitan), and polysorbate 80 (polyoxyethylene (20) sorbitan monooleate).

[0064] The numbers 20, 40, 60, and 80 following "polysorbate" indicate the fatty acid portions (lipophilic groups) attached to the polyoxyethylene sorbitan portion (the "hydrophilic group" of the molecule), where 20 is monolaurate, 40 is monopalmitic acid, 60 is monostearic acid, and 80 is monooleic acid (an example of a monounsaturated fatty acid portion).

[0065] The name "polysorbate#" refers to a sorbate to which 20 oxyethylene moieties [-(CH2CH2O)-] have been added.

[0066] In certain embodiments, the sugar-type surfactant may be one or more of polysorbate 20, polysorbate 40, polysorbate 60, and / or polysorbate 80. For example, the surfactant may be polysorbate 60 or may include other polysorbates.

[0067] Alternatively, instead of the polysorbates mentioned above, surfactants, which are variants of the specific polysorbates mentioned above, may be used. For example, referring to equation (I), R 7 ~R 10 Two, three, or all of them are the linear fatty acid portion (R 7 ~R 10 (If there is any remaining, it may be hydrogen.) An example of this compound is R 7 ~R 10 These three are fatty acid portions of stearic acid, and R 7 ~R 10It also contains polyoxyethylene sorbitan tristrate, one of which is hydrogen.

[0068] The melt flow rate (MFR) of the above lubricant (A) is preferably 100 g / 10 min or more, more preferably 500 g / 10 min or more. There is no particular upper limit, but it is usually 100,000 g / 10 min. Within the above range, the processability improvement effect will be better. In this specification, MFR is measured in accordance with ASTM D 1238 under conditions of 190°C and a load of 2.16 kgf.

[0069] In the processing aid of this disclosure, the content of the lubricant (A) is preferably 1% by mass or more, more preferably 2% by mass or more, even more preferably 4% by mass or more, and also preferably 98% by mass or less, more preferably 70% by mass or less, even more preferably 40% by mass or less, and most preferably 10% by mass or less.

[0070] The above resin (B) contains structural units represented by the following formula 1. It is preferable that the above lubricant (A) does not contain these structural units. -X-(CR 1 R 2 ) n -Y-(CR 3 R 4 ) m -Z- (Formula 1) (In formula 1, X is a divalent group which may have a single bond or a functional group, Y and Z are each independently composed of at least one group selected from the group consisting of a single bond, -O-, -C(=O)-, -C(=O)O-, -OC(=O)O-, -C(=NR')-, -C(=NR')O-, -OC(=NR')O-, -S-, -S(=O)-, -S(=O)O-, -OS(=O)O-, -S(=O)2-, -S(=O)2O-, -OS(=O)2O-, -P(=O)-, -P(=O)O-, -OP(=O)O-, -P(=O)2-, -P(=O)2O-, -OP(=O)2O-, -NR'-, and -C(OR')R'- (wherein R' is independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms in each occurrence). R 1 , R 2 , R 3 and R 4 Each of these is independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. n and m are independent integers between 0 and 10. At least one of X, Y, and Z is -C(=O)-, -C(=O)O-, -OC(=O)O-, or -C(OR')R'-.

[0071] In equation 1 above, X is X 1 and X 2 A divalent group consisting of at least one selected from the group comprising, X 1 This is a group composed of at least one selected from the group consisting of -C(=O)-, -C(=NR')-, -S(=O)2-, -NR'-, -CR'R'-, and -C(OR')R'- (wherein R' is independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms in each occurrence). X 2 It is preferably an aromatic hydrocarbon group having 1 to 12 carbon atoms, which may have substituents.

[0072] In Formula 1 above, X is more preferably a divalent group comprising at least one selected from the group consisting of -C(=O)-, -CR'R'-, and -C(OR')R'- (wherein R' is independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms in each occurrence).

[0073] In Formula 1 above, R' is preferably a hydrogen atom or a hydrocarbon group having 1 to 7 carbon atoms in each instance, more preferably a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, and even more preferably a hydrogen atom or a hydrocarbon group having 1 carbon atom.

[0074] In Formula 1 above, it is preferable that Y and Z are each independently composed of at least one group selected from the group consisting of a single bond, -O-, -C(=O)-, -C(=O)O-, -C(=NR')-, -C(=NR')O-, -S-, -S(=O)2-, -S(=O)2O-, -NR'-, and -C(OR')R'- (wherein R' is independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms in each occurrence).

[0075] In the above formula 1, it is preferable that Y and Z are each independently composed of at least one group selected from the group consisting of a single bond, -O-, -C(=O)-, and -C(=O)O-.

[0076] In formula 1 above, R 1 , R 2 , R 3 and R 4 Each of these is preferably a hydrogen atom or a hydrocarbon group having 1 to 7 carbon atoms, more preferably a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, and even more preferably a hydrogen atom or a hydrocarbon group having 1 carbon atom.

[0077] n and m are each preferably integers between 0 and 8, more preferably between 0 and 6, even more preferably between 0 and 4, and particularly preferably between 0 and 2.

[0078] Examples of the above resin (B) include polylactic acid (PLA), polybutylene succinate (PBS), ethylene-vinyl alcohol copolymer (EVOH), and polybutylene succinate adipate (PBSA). The above resin (B) is preferably at least one selected from the group consisting of PLA, PBS, EVOH, and PBSA, more preferably at least one selected from the group consisting of PLA, PBS, and EVOH, and even more preferably at least one selected from the group consisting of PLA and EVOH.

[0079] Furthermore, resin (B) may contain structural units other than those represented by formula 1. Examples of structural units other than those represented by formula 1 include glycol compounds such as ethylene glycol, propylene glycol, butanediol, heptanediol, hexanediol, octanediol, nonanediol, decanediol, 1,4-cyclohexanedimethanol, neopentyl glycol, glycerin, pentaerythritol, bisphenol A, polyethylene glycol, polypropylene glycol, and polytetramethylene glycol; oxalic acid, adipic acid, sebacic acid, azelaic acid, dodecanedionic acid, malonic acid, glutaric acid, cyclohexanedicarboxylic acid, and terephthalate. Examples of structural units derived from dicarboxylic acids such as lic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, bis(p-carboxyphenyl)methane, anthracenedicarboxylic acid, 4,4'-diphenyl etherdicarboxylic acid, 5-sodium sulfisoisophthalic acid, and 5-tetrabutylphosphonium isophthalic acid; hydroxycarboxylic acids such as glycolic acid, hydroxypropionic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxycaproic acid, and hydroxybenzoic acid; and lactones such as caprolactone, valerolactone, propiolactone, undecalactone, and 1,5-oxepan-2-one.

[0080] In the above resin (B), the content of the structural unit represented by formula 1 is preferably 0.1% by mass or more, more preferably 1% by mass or more, even more preferably 10% by mass or more, and particularly preferably 20% by mass or more. Also preferably 99.9% by mass or less, more preferably 99% by mass or less, and even more preferably 95% by mass or less.

[0081] The ethylene content of the above ethylene-vinyl alcohol copolymer is preferably 10 mol% or more, more preferably 20 mol% or more, even more preferably 30 mol% or more, and also preferably 60 mol% or less, more preferably 50 mol% or less, and even more preferably 40 mol% or less. Within the above range, the processability improvement effect is better. In this specification, the ethylene content is determined by nuclear magnetic resonance (NMR) spectroscopy.

[0082] The above-mentioned ethylene-vinyl alcohol copolymer is preferably obtained by saponifying an ethylene-vinyl ester copolymer, and among these, the one obtained by saponifying an ethylene-vinyl acetate copolymer is particularly preferred.

[0083] The degree of saponification of the above ethylene-vinyl alcohol copolymer is preferably 80 to 100 mol%.

[0084] When copolymerizing ethylene and vinyl acetate, other fatty acid vinyl esters (such as vinyl propionate and vinyl pivalate) can also be used in combination. Furthermore, the ethylene-vinyl alcohol copolymer may contain 0.0002 to 0.2 mol% of a vinylsilane compound as a copolymer component. Examples of vinylsilane compounds include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri(β-methoxyethoxy)silane, and γ-methacrylateoxypropylmethoxysilane. Among these, vinyltrimethoxysilane and vinyltriethoxysilane are preferred.

[0085] When copolymerizing ethylene and vinyl acetate, it is also possible to include small amounts of monomers other than the fatty acid vinyl esters and vinylsilane compounds mentioned above, such as α-olefins like propylene, isobutylene, α-octene, and α-dodecene; unsaturated acids like acrylic acid, methacrylic acid, crotonic acid, maleic acid, and itaconic acid, or their anhydrides, salts, or mono- or dialkyl esters; nitriles like acrylonitrile and methacrylonitrile; amides like acrylamide and methacrylamide; olefin sulfonic acids like ethylene sulfonic acid, allyl sulfonic acid, and methallyl sulfonic acid, or their salts; alkyl vinyl ethers, vinyl ketones, N-vinylpyrrolidone, vinyl chloride, and vinylidene chloride.

[0086] The melting point of the above resin (B) is preferably 65°C or higher, more preferably 70°C or higher, even more preferably 75°C or higher, even more preferably 80°C or higher, and also preferably 190°C or lower, more preferably 185°C or lower, and even more preferably 180°C or lower. Within the above range, the improvement effect on processability is better. In this specification, the melting point is the temperature corresponding to the maximum value in the heat of fusion curve when the temperature is increased at a rate of 10°C / min using a differential scanning calorimetry (DSC) device.

[0087] The melt flow rate (MFR) of the above resin (B) is preferably 0.001 g / 10 min or more, more preferably 0.01 g / 10 min or more, even more preferably 0.05 g / 10 min or more, even more preferably 0.1 g / 10 min or more, and particularly preferably 0.5 g / 10 min or more. It is also preferably 500 g / 10 min or less, more preferably 300 g / 10 min or less, even more preferably 150 g / 10 min or less, even more preferably 40 g / 10 min or less, even more preferably 20 g / 10 min or less, and particularly preferably 10 g / 10 min or less. Within the above range, the improvement effect on processability is better. In this specification, MFR is measured in accordance with ASTM D 1238 under conditions of 190°C and a load of 2.16 kgf.

[0088] The weight-average molecular weight of the above resin (B) is preferably 80,000 or more, more preferably 100,000 or more, from the viewpoint of improving processability, and similarly preferably 400,000 or less, more preferably 350,000 or less. The weight-average molecular weight of the above resin (B) can be determined by gel permeation chromatography (GPC) using chloroform as the solvent, a Tosoh Corporation high-temperature SEC column (GMHHR-H series) as the column, a flow rate of 1.0 mL / min, a column temperature of 40°C, a differential refractive index detector (RI) as the detector, and polystyrene having a known molecular weight as the reference.

[0089] In the processing aid of this disclosure, the content of the resin (B) is preferably 1% by mass or more, more preferably 30% by mass or more, even more preferably 60% by mass or more, and also preferably 99% by mass or less, more preferably 98% by mass or less, and even more preferably 96% by mass or less.

[0090] The processing aid of this disclosure may contain other components besides the lubricant (A) and the resin (B) described above. Other components include other additives (E). Other additives (E) include synergists, which are at least one selected from the group consisting of polyols with a melting point of 80°C or less, polycaprolactone, silicone, and polyamide-polyether block copolymers.

[0091] The melting point of the polyol described above should be 80°C or lower, but preferably 75°C or lower, more preferably 70°C or lower, even more preferably 68°C or lower, and also preferably 10°C or higher, more preferably 20°C or higher, and even more preferably 25°C or higher. Within the above range, the effect of improving processability will be better.

[0092] The above polyols are, for example, A[(OR 11 ) x2 Ure 12 ] y2 It can be expressed as follows, where A is usually an alkylene having one or more ether bonds, and y2 is 2 or 3, (OR 11 ) x2 OR is an oxyalkylene group. 11 A poly(oxyalkylene) chain having multiple (x2) R 11 Each of these is independently a C2-C5 alkylene, and in some embodiments, it is a C2-C3 alkylene, R 12 is hydrogen, alkyl, aryl, arylalkenyl, alkylallyrenyl, -C(O)-alkyl, -C(O)-aryl, -C(O)-arylalkenyl or -C(O)-alkylallyrenyl, where -C(O)- is OR 12 It is bonded to O. x² is between 10 and 230,000.

[0093] The above polyol is R 11 is a homopolymer of poly(oxyethylene) in which -CH2CH2- or R 11 is a homopolymer of poly(oxypropylene) in which -C3H6- and the like can be used.

[0094] The above polyol is a chain of randomly distributed oxyalkylene groups (for example, -OC2H4- and -OC3H6- units which are copolymers), or an alternating block consisting of repeating oxyalkylene groups (for example, (-OC2H4-) a1 block and (-OC3H6-) b1 block, and a1 + b1 is a polymer having a chain of 10 to 230,000) can also be used. <00>

[0095] In some embodiments of the above polyol, A is ethylene, -CH2-CH(-)-CH2- (derived from glycerol), CH3CH2C(CH2-)3 (derived from 1,1,1-trimethylolpropane), poly(oxypropylene), -CH2CH2-O-CH2CH2- or -CH2CH2-O-CH2CH2-O-CH2CH2-, and R 2 is hydrogen, methyl, butyl, phenyl, benzyl, acetyl, benzoyl or stearyl.

[0096] The above polyol is a polyester prepared from a dicarboxylic acid and a poly(oxyalkylene) polymer represented by A[(OR 11 ) x2 OR 12 ` y2 where A, R 11 and x2 are as defined above, and R 12 is hydrogen and y2 is 2 may also be in the form.

[0097] The above polyol may be used alone or in combination of two or more. From the viewpoint of excellent effect of improving processability, polyethylene glycol and polyethylene oxide are preferred, and polyethylene glycol is particularly preferred.

[0098] The number-average molecular weight (Mn) of the polyethylene glycol is preferably 1,000 or more, more preferably 3,000 or more, even more preferably 5,000 or more, and also preferably 50,000 or less, more preferably 45,000 or less, and even more preferably 40,000 or less. Within the above range, the improvement effect on processability is better. In this specification, the number-average molecular weight is calculated from the hydroxyl value measured in accordance with JIS K0070.

[0099] The viscosity-average molecular weight (Mv) of the polyethylene oxide is preferably 100,000 or more, more preferably 120,000 or more, even more preferably 140,000 or more, and also preferably 10,000,000 or less, more preferably 1,600,000 or less, and even more preferably 500,000 or less. Within the above range, the improvement effect on processability is better. In this specification, the viscosity-average molecular weight is calculated as follows: Using an Ostwald viscometer, the specific viscosity ηsp of aqueous solutions with various polymer concentrations c (g / dl) in pure water is measured at 35°C. Based on the relationship between the reduced viscosity (ηsp / c), obtained by dividing the specific viscosity by the polymer concentration, and the polymer concentration c, [η] is calculated by extrapolating the polymer concentration c to 0. Inserting [η] into the following formula, the viscosity-average molecular weight M is calculated. Formula: [η] = 6.4 × 10 -5 M 0.82

[0100] The polycaprolactone described above may be a homopolymer of ε-caprolactone or a modified polycaprolactone. Examples of the modified polycaprolactone include those obtained by modifying ε-caprolactone in the presence of 1,4-butanediol or the like during ring-opening polymerization, or those obtained by modifying the ends of the polymer with ether or ester groups.

[0101] The weight-average molecular weight (Mw) of the above polycaprolactone is preferably 2,000 or more, more preferably 10,000 or more, even more preferably 25,000 or more, and also preferably 100,000 or less, more preferably 95,000 or less, and even more preferably 90,000 or less. Within the above range, the improvement effect on processability is better. In this specification, the weight-average molecular weight is measured by gel permeation chromatography (GPC) on a polystyrene basis.

[0102] The melting point of the polycaprolactone is preferably 80°C or lower, more preferably 75°C or lower, even more preferably 70°C or lower, and even more preferably 68°C or lower, and also preferably 10°C or higher, more preferably 20°C or higher, and even more preferably 45°C or higher. Within the above range, the effect of improving processability is better.

[0103] The above silicones can, in principle, be any organosilicon compounds known to those skilled in the art by the term silicone polymers. A proper definition of silicone can be found in Winnacker / Kuchler: "Chemical Technology", edited by R. Dittmeyer, W. Keim, G. Kreysa, and A. Oberholz, Vol. 5: "Organic Intermediates, Polymers", Chapter: "Silicones", Wiley-VCH, Weinheim, 2005.

[0104] The silicone can be a substituted or unsubstituted linear oligo or polydiorganosiloxane, a branched silicone polymer, a silicone resin, or a crosslinked silicone polymer. Naturally, mixtures of various silicone polymers can also be used. As already mentioned, silicone-containing copolymers, such as polyether-functionalized silicones, silicone block copolymers with silicones or organic polymers containing urea or urethane units, can also be used. For better additiveity, the use of high molecular weight polydiorganosiloxanes is particularly preferred, which may also contain non-silicone components, such as fillers like fine particle silicic acid, chalk, talc, and sheet-like silicates.

[0105] Preferably, the silicone polymer corresponds to formula A, and [R 13 3SiO 1 / 2 ] a2 [SiR 13 20 2 / 2 ] b2 [R 13 SiO 3 / 2 ] c2 [SiO 4 / 2 ] d2 , here R 13 a2, b2, c2, and d2 are hydrogen, -OH, or unsubstituted or substituted C1 to C18 hydrocarbon residues, a2, b2, c2, and d2 each represent 0 or an integer, and a2+b2+c2+d2 is an integer from 5 to 15000.

[0106] C1 to C18 hydrocarbon residues R 13Examples of alkyl residues include methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, and tert-pentyl residues; hexyl residues, such as n-hexyl residues; heptyl residues, such as n-heptyl residues; octyl residues, such as n-octyl and isooctyl residues, such as 2,2,4-trimethylpentyl residues; nonyl residues, such as n-nonyl residues; decyl residues, such as n-decyl residues; cycloalkyl residues, such as cyclopentyl, cyclohexyl, 4-ethylcyclohexyl and cycloheptyl residues; norbornyl and methylcyclohexyl residues. Among alkyl residues, C1 to C6 residues, such as methyl and ethyl residues, with methyl residues being particularly preferred.

[0107] R 13 Examples also include unsaturated C1 to C18 hydrocarbon residues, e.g., alkenyl residues, e.g., vinyl residues, 2-propen-2-yl residues, allyl residues, 3-buten-1-yl residues, 5-hexen-1-yl residues, 10-undecen-1-yl residues, and cycloalkenyl residues (2-cyclohexenyl residues, 3-cyclohexenyl residues, cyclopentadienyl residues, 2-(cyclohexa-3-en-1-yl)ethyl residues); aryl residues, e.g., phenyl residues, biphenylyl residues, and naphthyl residues; alkaryl residues, e.g., o-, m-, and p-tolyl residues, and phenethyl residues (2-phenylethyl residues, 1-phenylethyl residues); and aralkyl residues, e.g., benzyl residues. Preferred unsaturated C1 to C18 hydrocarbon residues R 13 These are vinyl residues and phenyl residues.

[0108] residue R 13 Examples of substituted hydrocarbon residues include halogenated hydrocarbons, such as chloromethyl, 3-chloropropyl, 3-bromopropyl, 3,3,3-trifluoropropyl, and 5,5,5,4,4,3,3-heptafluoropentyl residues, as well as chlorophenyl, dichlorophenyl, and trifluorotolyl residues.

[0109] residue R 13 Preferably, it bonds to the silicone polymer represented by formula A via Si-C bonds, but it can also bond to the silicone polymer via oxygen atoms -O-.

[0110] R 13 It preferably has 1 to 6 carbon atoms. Ethyl residues, phenyl residues, vinyl residues, and methyl residues are particularly preferred.

[0111] Preferably, a2 + b2 + c2 + d2 means a number of at least 10, more preferably at least 100, particularly preferably at least 1000 and at most 15000, more preferably at most 10000, and particularly preferably at most 7000.

[0112] Preferably, c² + d² means < 0.1 × (a² + b² + c² + d²), and in particular, c² + d² < 0.05 × (a² + b² + c² + d²).

[0113] Preferably, all residues R 13 At least 50%, more preferably at least 70%, and especially preferably at least 80% of the residues are methyl residues.

[0114] In principle, all silicone polymers corresponding to formula A can be used. However, silicone polymers having a dynamic viscosity exceeding 1000 mPa.s, as measured according to DIN EN ISO 3219:1994 and DIN 53019, are preferred, using an Anton Paar "MCR 302" rheometer with an opening angle of 2° and a diameter of 50 mm (cone CP50-2), a measurement temperature of 25.00°C ± 0.05°C, and a shear rate of 1 sec⁻¹.

[0115] Among silicones, silicone polymers with very high molecular weights, such as UHMW polysiloxane (ultra-high molecular weight; described by KJRyan et al., Journal of Vinyl & Additive Technology, March 2000, Vol. 6, No. 1, pp. 7 to 19), may also be used.

[0116] The degree of polymerization of UHMW polysiloxane ranges from >1000 to approximately 14000, which corresponds to a number-average molecular weight between 74 kg / mol and 1000 kg / mol.

[0117] Typical UHMW polysiloxanes have a dynamic viscosity between 10 kPa.s and 50 kPa.s, preferably between 15 kPa.s and 30 kPa.s, measured with an airborne rotational rheometer according to DIN EN ISO 3219:1994 and DIN 53019, using a plate-plate system (25 mm diameter) with a 0.5 mm measurement gap. The measurement temperature is 25.00 °C ± 0.1 °C. The shear rate gradient is 0.1 sec. -1 The viscosity is described as the arithmetic mean of three independent measurements.

[0118] Because it is inexpensive and effective, among the above UHMW polysiloxanes, high molecular weight polydimethylsiloxanes having a dynamic viscosity between 1 kPa.s and 50 kPa.s, preferably between 10 and 40 kPa.s, and particularly preferably between 15 and 30 kPa.s (preferably measured by the method described above) are particularly preferred.

[0119] The above UHMW polysiloxanes include commercially available UHMW polysiloxanes such as MULTIBASE® MB50-001 and MULTIBASE® MB50-002 from Dupont, and GENIOPLAST® PELLET S, GENIOPLAST® PELLET P PLUS, GENIOPLAST® PE50S08, GENIOPLAST® PP50S12 and mixtures thereof from Asahi Kasei Wacker Silicone Co., Ltd., with MB50-002 and GENIOPLAST® PELLET S being preferred.

[0120] Silicone polymers are commercially available in pellet / granule or masterbatch form for immediate use, and can, for example, be mixed with thermoplastic granules before further processing.

[0121] The above-described polyamide-polyether block copolymer is a copolymer having polyamide blocks and polyether blocks in its polymer backbone. In this disclosure, such a block copolymer having polyamide blocks and polyether blocks may also be called a "polyamide / polyether block copolymer." It can also be abbreviated as "PEBA copolymer" or "PEBA." In some embodiments of this disclosure, the PEBA copolymer can be represented by the following general formula. [ka]

[0122] Here, PA represents the length of the polyamide block, PE represents the length of the polyether block, and p represents the total number of polyamide and polyether blocks. In some embodiments of this disclosure, the polyether block can be represented by the following general formula. [ka]

[0123] Here, EG is the first unspecified terminal group, B is the unspecified crosslinking group, and EG * This is the second unspecified terminal group, EG, B and EG * The length is determined by the synthesis method used to produce the PEBA copolymer. Here, n2 represents the length of the polyamide block, x3 represents the length of the amide component within the polyamide block, m1 represents the length of the poly(ether) block, y3 represents the length of the ether component within the poly(ether) block, and p represents the length of the PEBA copolymer and the total number of polyamide and polyether blocks. In some embodiments of this disclosure, the PEBA copolymer can be represented by the following general formula. [ka]

[0124] Here, n2 represents the length of the polyamide block, x3 represents the length of the amide component within the polyamide block, m1 represents the length of the poly(ether) block, y3 represents the length of the ether component within the poly(ether) block, p represents the length of the PEBA copolymer, and the total number of polyamide and polyether blocks is shown.

[0125] The polyamide block in the above PEBA copolymer is derived from polyamide-12 (PA-12), polyamide-11 (PA-11), polyamide-6 (PA-6), or polyamide-66 (PA-66).

[0126] The weight-average molecular weight (e.g., Mw and Mn) of a PEBA copolymer can be measured, for example, by gel permeation chromatography (i.e., size exclusion chromatography) using narrow molecular weight polymer standards with techniques known in the art.

[0127] In the embodiment, the number-average molecular weight Mn of the polyamide block in the PEBA copolymer is about 100 to about 15,000 g / mol, or about 300 to about 15,000 g / mol, or about 600 to about 10,000 g / mol, or about 600 to about 5,000 g / mol. The number-average molecular weight Mn of the polyether block in the above PEBA copolymer is approximately 100 to 15,000 g / mol, approximately 100 to 10,000 g / mol, approximately 100 to 6,000 g / mol, approximately 100 to 3,000 g / mol, approximately 200 to 6,000 g / mol, approximately 200 to 3,000 g / mol, approximately 250 to 2,000 g / mol, approximately 750 to 3,500 g / mol, or approximately 1,000 to 3,000 g / mol.

[0128] The number-average molecular weight Mn of the above PEBA copolymer ranges from 10,000 to 500,000 g / mol, including subranges within this range and any number within this range. For example, in embodiments of the present disclosure, the number-average molecular weight Mn of the PEBA copolymer is 10,000 to 400,000 g / mol, or 10,000 to 300,000 g / mol, 10,000 to 250,000 g / mol, or 15,000 to 300,000 g / mol, or 20,000 to 300,000 g / mol, or 15,000 to 200,000 g / mol, or 20,000 to 200,000 g / mol, or 30,000 to 250,000 g / mol, or about 25,000 to about 75,000 g / mol, or about 50,000 to about 75,000 g / mol, or about 100,000 to about 150,000 g / mol. The number-average molecular weight Mn of the above PEBA copolymer is at least 10,000 g / mol, at least 20,000 g / mol, at least 25,000 g / mol, greater than 25,000 g / mol, at least 30,000 g / mol, greater than 30,000 g / mol, at least 35,000 g / mol, greater than 35,000 g / mol, at least 50,000 g / mol, or greater than 50,000 g / mol.

[0129] In embodiments, the weight-average molecular weight Mw of the PEBA copolymer is 25,000 to 500,000 g / mol, including subranges within this range and any number within this range. For example, in embodiments of the present disclosure, the weight-average molecular weight Mw of the PEBA copolymer is about 100,000 to about 250,000 g / mol, or about 100,000 to about 150,000 g / mol, or about 125,000 to about 150,000 g / mol. The polyamide and polyether blocks within the PEBA copolymer described above can be randomly distributed.

[0130] The above PEBA copolymer comprises a polyamide block and a polyether block, the polyamide block may account for at least 50% by mass of the copolymer. Furthermore, the PEBA copolymer comprises a polyamide block and a polyether block, and the molar ratio of the polyamide block to the polyether block may be in the range of 1:3 to 3:1, or 1:2 to 2:1, or 3:2 to 1:3, or 2:3 to 3:1, or about 1:1.

[0131] By reacting the above-mentioned polyamide and polyether block precursors, PEBA copolymers having polyamide blocks and polyether blocks can be prepared. For example, by reacting a lactam, a polyetherdiol, and a chain-limiting diacid together in the presence of a small amount of water, a PEBA copolymer having polyamide blocks and polyether blocks of variable length and statistically random distribution within the block copolymer chain can be obtained. The above polyether blocks may be derived from poly(oxyethylene), poly(oxypropylene), or poly(tetramethylene ether) glycol, each of which may spontaneously co-condense with a polyamide block containing carboxylic acid chain ends. Chain limiting agents may also be present during the polycondensation reaction to give a PEBA copolymer containing polyamide and polyether blocks randomly distributed within the block copolymer. The above polyether blocks are derived from poly(oxyethylene), poly(oxypropylene), or poly(tetramethylene ether) glycols, which are first converted to polyetherdiamines by amination and then co-condensed with polyamide blocks containing carboxylic acid chain ends. Chain limiting agents are also present during the polycondensation reaction to give a PEBA copolymer containing polyamide and polyether blocks randomly distributed within the block copolymer. The above polyether block can be derived from poly(oxyethylene), also known as polyethylene glycol (PEG). The above polyether block can be derived from poly(oxypropylene), also known as polypropylene glycol (PPG). The above polyether blocks can be derived from poly(tetramethylene ether) glycol (PTMG), also known as polytetramethylene oxide (PTMEO) or polytetrahydrofuran (PTHF).

[0132] The above PEBA copolymer comprises i) a polyamide block selected from polyamide-12 (PA-12), polyamide-11 (PA-11), polyamide-6 (PA-6), or a mixture thereof, and ii) a polyether block selected from polyethylene glycol (PEG), polypropylene glycol (PPG), polytetrahydrofuran (PTHF), or a mixture thereof.

[0133] The PEBA copolymer comprises i) a polyamide block selected from polyamide-12 (PA-12), polyamide-11 (PA-11), polyamide-6 (PA-6), or a mixture thereof, and ii) a polyether block which is polyethylene glycol (PEG). In one embodiment of the present disclosure, the PEBA copolymer comprises i) a polyamide block which is polyamide-12 (PA-12), and ii) a polyether block which is polyethylene glycol (PEG).

[0134] The above PEBA copolymer comprises 10 to 20 polyamide blocks and 10 to 20 polyether blocks.

[0135] The above PEBA copolymer contains only one type of polyamide block and one type of polyether block.

[0136] The above PEBA copolymer comprises i) a polyamide block which is polyamide-12 (PA-12), and ii) a polyether block which is polyethylene glycol (PEG), where the polyamide-12 block accounts for approximately 30% to 70% by mass of the copolymer, and the polyethylene glycol block accounts for approximately 70% to 30% by mass of the copolymer.

[0137] The above PEBA copolymer comprises i) a polyamide block which is polyamide-12 (PA-12), and ii) a polyether block which is polyethylene glycol (PEG), where the polyamide-12 block accounts for approximately 40% to 60% by mass of the copolymer, and the polyethylene glycol block accounts for approximately 60% to 40% by mass of the copolymer.

[0138] The above PEBA copolymer comprises i) a polyamide block which is polyamide-12 (PA-12) and ii) a polyether block which is polyethylene glycol (PEG), where the polyamide-12 block represents about 45% by mass of the copolymer and the polyethylene glycol block represents about 55% by mass of the copolymer.

[0139] The above PEBA copolymer comprises i) 10 to 20 polyamide blocks which are polyamide-12 (PA-12), and ii) 10 to 20 polyether blocks which are polyethylene glycol (PEG).

[0140] The above PEBA copolymer comprises i) a polyamide block which is polyamide-12 (PA-12), and ii) a polyether block which is polyethylene glycol (PEG), with a number average molecular weight Mn of approximately 25,000 to approximately 75,000 g / mol.

[0141] The above PEBA copolymer comprises i) a polyamide block which is polyamide-12 (PA-12) and ii) a polyether block which is polyethylene glycol (PEG), with a number average molecular weight Mn of approximately 50,000 to approximately 75,000 g / mol. The above PEBA copolymer comprises i) a polyamide block which is polyamide-12 (PA-12) and ii) a polyether block which is polyethylene glycol (PEG), with a number average molecular weight Mn of approximately 66,100 g / mol.

[0142] The above PEBA copolymer comprises i) a polyamide block which is polyamide-12 (PA-12), and ii) a polyether block which is polyethylene glycol (PEG), with a weight-average molecular weight Mw of approximately 100,000 to approximately 150,000 g / mol.

[0143] The above PEBA copolymer comprises i) a polyamide block which is polyamide-12 (PA-12), and ii) a polyether block which is polyethylene glycol (PEG), with a weight-average molecular weight Mw of approximately 125,000 to approximately 150,000 g / mol.

[0144] The above PEBA copolymer comprises i) a polyamide block which is polyamide-12 (PA-12) and ii) a polyether block which is polyethylene glycol (PEG), and has a weight-average molecular weight Mw of approximately 134,000 g / mol.

[0145] In one embodiment of the present disclosure, the PEBA copolymer comprises i) a polyamide block which is polyamide-6 (PA-6), and ii) a polyether block which is polyethylene glycol (PEG). The above PEBA copolymer comprises i) a polyamide block which is polyamide-6 (PA-6) and ii) a polyether block which is polyethylene glycol (PEG), where the polyamide-6 block represents about 30% to 60% by mass of the copolymer, and the polyethylene glycol block represents about 70% to 40% by mass of the copolymer.

[0146] The above PEBA copolymer comprises i) a polyamide block which is polyamide-6 (PA-6) and ii) a polyether block which is polyethylene glycol (PEG), where the polyamide-6 block represents approximately 50% to 35% by mass of the copolymer, and the polyethylene glycol block represents approximately 50% to 65% by mass of the copolymer.

[0147] The above PEBA copolymer comprises i) 10 to 20 polyamide blocks which are polyamide-6 (PA-6), and ii) 10 to 20 polyether blocks which are polyethylene glycol (PEG).

[0148] The above PEBA copolymer comprises i) a polyamide block which is polyamide-11 (PA-11), and ii) a polyether block which is polyethylene glycol (PEG). In one embodiment of the present disclosure, the PEBA copolymer comprises i) a polyamide block which is polyamide-12 (PA-12), and ii) a polyether block which is polytetrahydrofuran (PTHF).

[0149] The above PEBA copolymer comprises i) a polyamide block which is polyamide-12 (PA-12), and ii) a polyether block which is polytetrahydrofuran (PTHF), where the polyamide-12 block represents approximately 75% to 10% by mass of the copolymer, and the polytetrahydrofuran block represents approximately 25% to 90% by mass of the copolymer.

[0150] The above PEBA copolymer comprises i) a polyamide block which is polyamide-12 (PA-12), and ii) a polyether block which is polytetrahydrofuran (PTHF), where the polyamide-12 block represents about 80% to 60% by mass of the copolymer, and the polytetrahydrofuran block represents about 20% to 40% by mass of the copolymer.

[0151] The above PEBA copolymer comprises i) a polyamide block which is polyamide-12 (PA-12), and ii) a polyether block which is polytetrahydrofuran (PTHF), where the polyamide-12 block represents about 40% to 60% by mass of the copolymer, and the polytetrahydrofuran block represents about 60% to 40% by mass of the copolymer.

[0152] The above PEBA copolymer comprises i) a polyamide block which is polyamide-12 (PA-12), and ii) a polyether block which is polytetrahydrofuran (PTHF), where the polyamide-12 block represents approximately 30% to 10% by mass of the copolymer, and the polytetrahydrofuran block represents approximately 70% to 90% by mass of the copolymer. The above PEBA copolymer comprises i) 10 to 20 polyamide blocks which are polyamide-12 (PA-12), and ii) 10 to 20 polyether blocks which are polytetrahydrofuran (PTHF).

[0153] The above PEBA copolymer comprises i) a polyamide block which is polyamide-12 (PA-12) and ii) a polyether block which is polytetrahydrofuran (PTHF), and has a number-average molecular weight Mn of approximately 25,000 to approximately 75,000 g / mol. The above PEBA copolymer comprises i) a polyamide block which is polyamide-12 (PA-12) and ii) a polyether block which is polytetrahydrofuran (PTHF), with a number average molecular weight Mn of about 40,000 to about 60,000 g / mol. In embodiments of the present disclosure, the PEBA copolymer comprises i) a polyamide block which is polyamide-12 (PA-12) and ii) a polyether block which is polytetrahydrofuran (PTHF), with a number average molecular weight Mn of about 50,000 g / mol.

[0154] The above PEBA copolymer comprises i) a polyamide block which is polyamide-6 (PA-6), and ii) a polyether block which is polytetrahydrofuran (PTHF). The above PEBA copolymer comprises i) a polyamide block which is polyamide-11 (PA-11), and ii) a polyether block which is polytetrahydrofuran (PTHF). The above-mentioned PEBA copolymer is a commercially available elastomer sold under the trade name PEBAX®.

[0155] The above PEBA copolymer is a commercially available elastomer selected from the group consisting of: PEBAX 2533 SA 01, PEBAX 2533 SA 01 MED, PEBAX 2533 SD 02, PEBAX 3533 SA 01, PEBAX 3533 SA 01 MED, PEBAX 3533 SP01, PEBAX 4011, PEBAX 4033 SA 01, PEBAX 4033 SA 01 MED, PEBAX 4033 SP01, PEBAX 4533 SA 01, PEBAX 4533 SA 01 MED, PEBAX 4533 SP01, PEBAX 5513 SA 01, PEBAX 5513 SP01, PEBAX 5533 SA 01, PEBAX 5533 SA 01 MED, PEBAX 5533 SN 70 BLACK, PEBAX 5533 SP01, PEBAX SA 01, PEBAX 6333 SA 01 MED, PEBAX SP01, PEBAX 6333 SP01, PEBAX 6333 SA 01, PEBAX, PEBAX 3533 SA 01, PEBAX 3533 SA 01 MED, PEBAX 3533 SP01, PEBAX 4011 SA 01, PEBAX 4033 SA 01 MED, PEBAX 4033 SP01, PEBAX 4033 SA 01 MED, PEBAX Clear 2533, PEBAX ES 2533 UV, PEBAX MH 2533, PEBAX MH2030, PEBAX MV 5513 SA 01, PEBAX MV 5513 Examples include SA 01 MED, PEBAX MV 5533 SP01, PEBAX MV 5533, PEBAX MV 5533 SP01, PEBAX RNEW (registered trademark) 30R51 SA 01, PEBAX RNEW 35R53 SP01, PEBAX RNEW 70R53 SP01, PEBAX RNEW 55R53 SP01, PEBAX RNEW 63R53 SP01, PEBAX RNEW 70R53 SP01, PEBAX RNEW 70R53 SP01, PEBAX, PEBAX RNEW 72R53 SP01, PEBAX RNEW 80R53 SP 02, and mixtures thereof. The above-mentioned PEBA copolymer is a commercially available elastomer and is sold under the trademark names VESTAMID® or VESTAMID E.

[0156] The above PEBA copolymer is a commercially available elastomer selected from the group consisting of VESTAMID D, VESTAMID DX, VESTAMID E, VESTAMID EX, VESTAMID Care, VESTAMID Care ML, VESTAMID Care ME, VESTAMID Care ME-B, VESTAMID L, VESTAMID LX, VESTAMID NRG, VESTAMID Terra, VESTAMID X, and mixtures thereof. Among these, Pebax MV1072 is preferred.

[0157] The above PEBA copolymer can be used in the form of a semi-solid or viscous liquid, or as a powder, pellet or granule.

[0158] In the processing aid of this disclosure, the content of the synergist is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 1% by mass or more, and also preferably 99% by mass or less, more preferably 70% by mass or less, and even more preferably 40% by mass or less.

[0159] In the processing aid of this disclosure, the total amount of the lubricant (A) and the resin (B), and the mass ratio of the synergist (lubricant (A) + resin (B): synergist) are, A mass ratio of 99.9:0.1 to 10:90 is preferred. The above mass ratio is more preferably 99.5:0.5 to 30:70, even more preferably 99:1 to 50:50, and particularly preferred 98:2 to 60:40.

[0160] Other components may include, for example, anti-sticking agents; UV absorbers; flame retardants; reinforcing materials such as glass fibers and glass powder; stabilizers such as minerals and flakes; lubricants such as silicone oil and molybdenum disulfide; pigments such as titanium dioxide and red iron oxide; conductive agents such as carbon black; impact-resistant agents such as rubber; antioxidants such as hindered phenols and phosphorus-based antioxidants; and nucleating agents and antiblocking agents such as metal salts and sorbitol acetals.

[0161] In the processing aid of this disclosure, the mass ratio of the lubricant (A) to the resin (B) (lubricant (A):resin (B)) is preferably 1:99 to 99:1, more preferably 2:98 to 40:60, and most preferably 4:96 to 10:90.

[0162] From the viewpoint of excellent storage stability, it is preferable to use multiple resins (B). In this case, it is preferable to use EVOH (resin (B1)) and resins other than EVOH (B) (resin (B2)) in combination. Resin (B2) is not particularly limited, but it is preferably PLA or PBS, and more preferably PLA. That is, it is preferable to use resin (B) in combination with EVOH and PLA and / or PBS, and more preferably EVOH and PLA in combination.

[0163] The mass ratio of the above lubricant (A), resin (B1), and resin (B2) (lubricant (A): resin (B1): resin (B2)) is preferably 1-98:1-98:1-98, more preferably 2-70:5-73:25-93, and most preferably 4-18:10-24:72-86.

[0164] In the processing aid of this disclosure, the total content of the lubricant (A), the resin (B), and the synergist is preferably 25% by mass or more, more preferably 35% by mass or more, even more preferably 55% by mass or more, and particularly preferably 85% by mass.

[0165] The processing aids of this disclosure are preferably substantially fluorine-free. "Substantially fluorine-free" means that the fluorine content in the processing aid is 10 ppm or less (preferably 1 ppm or less, more preferably 0.1 ppm or less). The processing aids of this disclosure are particularly preferably fluorine-free (fluorine content is 0% by mass).

[0166] The moisture content of the processing aid is preferably 1.0% by mass or less, more preferably 0.5% by mass or less, even more preferably 0.2% by mass or less, and most preferably 0.1% by mass or less. The lower limit is not particularly limited and may be 0% by mass.

[0167] In this specification, the moisture content is measured by the following method. The mass of the processing aid is measured before and after heating at 130°C for 24 hours, and the result is calculated according to the following formula. Three samples are taken, and the calculation is performed for each sample. The average value is then calculated and adopted. Moisture content (mass %) = [(Mass of processing aid before heating (g)) - (Mass of processing aid after heating (g))] / (Mass of processing aid before heating (g)) × 100

[0168] The method for obtaining a processing aid with a moisture content within the above range is not particularly limited. For example, a material with a low moisture content may be used, and the processing aid may be prepared under dry conditions. Alternatively, a processing aid may be prepared using ordinary materials and conditions, and then moisture may be removed by heat treatment or the like.

[0169] The processing aid of this disclosure may be obtained, for example, by a mixing step in which the lubricant (A) and the resin (B) are put into a mixer or the like and mixed, and a dispensing step in which the mixture is discharged from the mixer or the like. This disclosure also relates to a method for producing the above-mentioned processing aid, including the mixing step and the dispensing step.

[0170] The method of the above mixing process is not particularly limited, and may be mixing (kneading) with shear force applied, or mixing without shear force applied. Among these, kneading is preferred, and melt kneading is more preferred, in order to effectively exhibit the above-mentioned moldability. Furthermore, when melt-mixing is performed, each component may be melted during the mixing process, or it may be melted before the mixing process.

[0171] In the above manufacturing method, a molding process may be performed after the extrusion process, in which the extruded material is molded using a molding machine or the like. The molding process described above is not particularly limited and can include, for example, extrusion molding, injection molding, blow molding, etc., but among these, extrusion molding is preferred in order to effectively exhibit the above-mentioned moldability.

[0172] An extruder is used for the above extrusion molding. Examples of such extruders include single-screw extruders, twin-screw extruders, and tandem extruders. The extruder typically comprises a cylinder, a screw housed within the cylinder, a die attached to the tip of the cylinder, and a hopper for supplying pellets to the cylinder.

[0173] The above-mentioned conditions for molding are not particularly limited and can be set as appropriate depending on the composition and quantity of the composition, the desired shape and size of the molded product, etc.

[0174] The processing aids of this disclosure are particularly useful as processing aids for thermoplastic resins (especially polyolefin resins).

[0175] <Masterbatch> The masterbatch of this disclosure comprises the processing aid of this disclosure and a thermoplastic resin (C). The processing aids disclosed herein may be added directly to the target material, such as a thermoplastic resin, or they may be in the form of a masterbatch. Adding them in the form of a masterbatch provides metering stability and good dispersibility.

[0176] Examples of the thermoplastic resin (C) mentioned above include polyolefin polymers (polyethylene (PE)-polypropylene (PP)-ethylene-propylene copolymer), polystyrene (PS), AS (acrylonitrile styrene) resin (AS), ABS (acrylonitrile butadiene styrene) resin (ABS), methacrylic resin (PMMA), polymethylpentene (PMP), butadiene resin (BDR), polybutene-1 (PB-1), polyvinyl alcohol (PVA), polyacrylonitrile (PAN), polymethacrylic styrene (MS), ethylene vinyl acetate copolymer (EVA), ethylene-vinyl alcohol copolymer, and polyvinyl chloride (PVC). These may be used individually or in combination of two or more. Polyolefin polymers (polyolefin resins) are preferred because they provide a better improvement in processability.

[0177] Among polyolefin polymers, examples include homopolymers (e.g., C2-C10α-olefin homopolymers, preferably C2-C6α-olefin homopolymers). Specific examples of homopolymers include homopolyethylene and polypropylene (hPP). For example, taking homopolyethylene as an example, such polymers can be produced, for example, by free radical polymerization in a high-pressure process, and are typically highly branched ethylene homopolymers, often known as LDPE (low-density polyethylene), with a density of 0.945 g / cm³. 3 Less than 0.935 g / cm³ 3 For example, 0.900, 0.905, or 0.910 g / cm³. 3 From 0.920, 0.925, 0.927, 0.930, 0.935, or 0.945 g / cm³ 3 It is within the range. Unless otherwise stated herein, all polymer density values ​​are determined according to ASTM D1505. Samples are molded under ASTM D4703-10a, procedure C, and allowed to stand for 40 hours under ASTM D618-08 (23±2°C and relative humidity 50±10%) before testing.

[0178] In another example, ethylene monomers can be polymerized using known gas, slurry, and / or solution phase polymerization, for example, catalysts such as chromium-based catalysts, or single-site catalysts such as Ziegler-Natta and / or metallocene catalysts, all of which are well known in polymerization techniques and will not be discussed further herein. When a more linear ethylene homopolymer is produced (e.g., using gas-phase or slurry-phase polymerization with any of the catalysts mentioned above), it is called HDPE (high-density polyethylene) and is typically 0.945 to 0.970 g / cm³. 3 Within the range of 0.945 g / cm³, 3 It has the above density.

[0179] Further examples of polymers include copolymers of two or more C2-C40α-olefins, such as C2-C20α-olefins, such as ethylene-α-olefin copolymers, or propylene-α-olefin copolymers (e.g., propylene-ethylene copolymers or propylene-ethylene-diene ternpolymers (sometimes known as EPDM or PEDM)). Specific examples intended herein include copolymers of ethylene and one or more C3-C20α-olefin comonomers such as C4-C12α-olefin comonomers (1-butene, 1-hexene, 1-octene, or mixtures of two or more thereof are preferred in various embodiments). Ethylene copolymers (for example, copolymers of ethylene and one or more C3-C20α-olefins) can contain at least 90, 94, 95, or 96 wt% (for example, ranging from a low value of 80, 85, 90, 80, 85, 93, 93, 95, 96, or 97 wt% to a high value of 94, 95, 95.5, 91, 92, 97, 94, 97.5, or 98 wt%, and can contain at least 96 wt% or 96.5 wt% of ethylene-derived units, based on the total amount of ethylene-derived units and comonomer-derived units. For example, ethylene copolymers can contain at least 96 wt% or 96.5 wt% of ethylene-derived units, based on the total amount of ethylene-derived units and comonomer-derived units. The copolymer may contain 94 or 95% to 97 or 98% by mass of ethylene-derived units. The copolymer balance (based on ethylene-derived units and comonomer-derived units) consists of comonomer-derived units. For example, comonomer units (e.g., units derived from C2-C20α-olefins, such as units derived from butene, hexene, and / or octene) can be present in the ethylene copolymer in values ​​ranging from as low as 2, 2.5, 3, 3.5, 4, 4.5, 5, or 6% by mass to as high as 3, 4, 5, 6, 7, 8, 9, 10, 15, or 20% by mass, with the range being from the lower values ​​to the intended higher values ​​(provided the higher values ​​are greater than the lower values).

[0180] While several suitable comonomers are already known for ethylene-based, propylene-based, or other α-olefin-based copolymers, other α-olefin comonomers are intended in various embodiments. For example, the α-olefin comonomers may be linear or branched, and two or more comonomers may be used as needed. Examples of suitable comonomers include linear C3-C20 α-olefins (such as butene, hexene, and octene, as already mentioned) and α-olefins having one or more C1-C3 alkyl branched or aryl groups. For example, comonomers include propylene; 3-methyl-1-butene; 3,3-dimethyl-1-butene; 1-pentene; 1-pentene having one or more methyl, ethyl, or propyl substituents; 1-hexene having one or more methyl, ethyl, or propyl substituents; 1-heptene having one or more methyl, ethyl, or propyl substituents; 1-octene having one or more methyl, ethyl, or propyl substituents; 1-nonene having one or more methyl, ethyl, or propyl substituents; ethyl, methyl, or dimethyl substituted 1-decene; 1-dodecene; and styrene. The above list of comonomers is merely illustrative and not intended to limit them. In some embodiments, comonomers include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, and styrene.

[0181] In certain embodiments, the polymer may include or (as described above) be an ethylene copolymer. Ethylene copolymers can be produced by gas, slurry, or solution phase polymerization, and some particularly preferred ethylene copolymers can be produced by gas or slurry phase polymerization. Specific examples include linear low-density polyethylene (LLDPE), copolymers of ethylene with one or more α-olefins, which are polymerized in the presence of one or more single-site catalysts, e.g., one or more Ziegler-Natta catalysts, one or more metallocene catalysts, and combinations thereof. Such LLDPEs are available in concentrations of 0.900, 0.905, 0.907, and 0.910 g / cm³. 3From low concentrations to 0.920, 0.925, 0.930, 0.935, 0.940, or 0.945 g / cm³ 3 It can have a density within a high concentration range. LLDPE can be distinguished from the LDPE described above in several respects, many of which are well known in the art, including the degree of branching in the manufactured polymer (often negligible, if any), and it should be noted that LLDPE has substantially fewer long-chain branchings. In certain embodiments, the polymer of the polymer composition is or contains metallocene-catalyzed LLDPE (mLLDPE). In yet other embodiments, the polymer of the polymer composition is or contains Ziegler-Natta-catalyzed LLDPE (or Zn-LLDPE).

[0182] Furthermore, the polymer density ranges from 0.905 to 0.945 g / cm³ in some embodiments. 3 Within the range of 0.905, 0.907, 0.908, 0.910, 0.911, 0.912, 0.913, 0.914, or 0.915 g / cm³ 3 From any of the following lower values: 0.916, 0.917, 0.918, 0.919, 0.920, 0.924, 0.926, 0.930, 0.935, 0.940, or 0.945 g / cm³ 3 It is within the range of either the lower or higher of the above values, and that range is from the lower to the higher values ​​intended herein (for example, 0.910 to 0.925 or 0.935 g / cm³). 3 For example, 0.912 to 0.925 or 0.915 to 0.918 g / cm³ 3 ). In yet another embodiment, the polymer is 0.945 g / cm³. 3 From 0.970 g / cm³ 3 It may also be a higher density (e.g., HDPE) having a density within the range.

[0183] Furthermore, the rheological properties of the polymer can influence the processing aid composition used to form the molded product. Generally, the processing aid composition is preferably used in polymers having a melt index (MI or I2, measured at 190°C and a 2.16 kg load according to ASTM D1238) of 1.5 g / 2.0 min or less, preferably 2.5 g / 3.0 min or less, such as in the range of 0.1, 0.2, or 0.5 g / 10 min to 1.0, 1.2, 5.0, 10, 2.5, 10, 4.0, or 5.0 g / 10 min. The melt index ratio (MIR) (MIR is defined herein as the ratio of the high-load melt index (HLMI) (measured per ASTM D1238 at 190°C and a 21.6 kg load) to the melt index, or HLMI / MI) can be in the range of 10, 12, or 15 to 19, 20, 21, 22, 25, 27, 30, 35, 40, 45, 50, 60, 65, 70, 75, 80, 85, 90, 95, or 100 in polymers of some embodiments. If necessary, the MI in such polymers may be less than 1.5 g / 10 min, such as 1.0 g / 10 min or less (e.g., 0.1, 0.2, or 0.5 g / 10 min to 1.0; or any of 1.1, 1.2, 1.3, 1.4, or less than 1.5 g / 10 min).

[0184] Furthermore, the LLDPE is preferably at least one selected from the group consisting of Ziegler-Natta catalytic LLDPE and metallocene catalytic LLDPE. Metallocene catalytic LLDPE is particularly preferred.

[0185] The thermoplastic resin (C) described above may be crystalline or non-crystalline. If the thermoplastic resin (C) is crystalline, it is preferably one with a melting point of 80 to 300°C, and more preferably one with a melting point of 100 to 200°C. If the non-crystalline thermoplastic resin (C) is non-crystalline, it is preferable that it has a processing temperature approximately the same as that of the crystalline thermoplastic resin (C) with a specified melting point range.

[0186] In the masterbatch of this disclosure, the mass ratio of the thermoplastic resin (C) to the processing aid (thermoplastic resin (C): processing aid) is preferably 99:1 to 1:99. The mass ratio is more preferably 97:3 to 50:50, even more preferably 95:5 to 60:40, and particularly preferably 92:8 to 70:30.

[0187] In the masterbatch of this disclosure, the total content of the thermoplastic resin (C) and the processing aid is preferably 80% by mass or more, more preferably 90% by mass or more, even more preferably 95% by mass or more, and particularly preferably 100% by mass.

[0188] The melt flow rate (MFR) of the masterbatch of this disclosure is preferably 0.1 g / 10 min or more, more preferably 0.5 g / 10 min or more, even more preferably 1 g / 10 min or more, even more preferably 1.5 g / 10 min or more, and also preferably 100 g / 10 min or less, more preferably 50 g / 10 min or less, even more preferably 30 g / 10 min or less, even more preferably 20 g / 10 min or less, and particularly preferably 10 g / 10 min or less. Within the above range, the effect of improving processability is better.

[0189] The masterbatch of this disclosure may contain components other than the thermoplastic resin (C) and the processing aid described above. Other components besides the thermoplastic resin (C) and processing aids mentioned above include, for example, anti-sticking agents; ultraviolet absorbers; flame retardants; reinforcing materials such as glass fibers and glass powder; stabilizers such as minerals and flakes; lubricants such as silicone oil and molybdenum disulfide; pigments such as titanium dioxide and red iron oxide; conductive agents such as carbon black; impact-resistant agents such as rubber; antioxidants such as hindered phenols and phosphorus-based antioxidants; nucleating agents and antiblocking agents such as metal salts and sorbitol acetals; and the lubricant (A) mentioned above.

[0190] The masterbatch of this disclosure may be obtained, for example, by preparing the processing aid of this disclosure in advance and putting it into a mixer or the like with the thermoplastic resin (C) and performing a mixing step, and then discharging the mixture from the mixer or the like; or by putting the thermoplastic resin (C), the lubricant (A), and the resin (B) into a mixer or the like and performing a mixing step, and then discharging the mixture from the mixer or the like. This disclosure is also a method for manufacturing the masterbatch described above, including a mixing step and a discharging step.

[0191] In the method for manufacturing a masterbatch according to this disclosure, a molding step may be performed after the dispensing step in which the dispensed material is molded using a molding machine or the like.

[0192] The mixing, dispensing, and molding steps in the method for manufacturing the masterbatch of this disclosure are the same as those described in the method for manufacturing the processing aid of this disclosure. The shape of the masterbatch of this disclosure is not particularly limited and may be a powder, granules, pellets, etc., but pellets are preferred because they are easy to handle and easy to mold.

[0193] The masterbatch of this disclosure is particularly useful as a masterbatch for improving the processability of thermoplastic resins (especially polyolefin resins).

[0194] <Thermoplastic resin composition> The thermoplastic resin composition of this disclosure comprises the processing aid and / or the masterbatch of this disclosure and a thermoplastic resin (D). This provides good processability. In particular, good extrusion processability is obtained even during long-run molding. Furthermore, the storage stability of the extruded product is also excellent.

[0195] The thermoplastic resin (D) can be the same as the thermoplastic resin (C) and the preferred form is also the same. The masterbatch of this disclosure comprises the processing aid of this disclosure and the thermoplastic resin (C). The processing aid of this disclosure may be added directly to the object such as the thermoplastic resin, or it may be added in masterbatch form.

[0196] The thermoplastic resin composition of this disclosure may contain at least one of the processing aid and the masterbatch of this disclosure, but it is preferable to include the masterbatch of this disclosure in order to obtain better processability.

[0197] If the thermoplastic resin composition of the present disclosure includes the masterbatch of the present disclosure, the thermoplastic resin (C) and the thermoplastic resin (D) may be of the same type or of different types.

[0198] In the thermoplastic resin composition of this disclosure, the content of the processing aid is preferably 0.001% by mass or more, more preferably 0.02% by mass or more, even more preferably 0.04% by mass or more, particularly preferably 0.06% by mass or more, and also preferably 3% by mass or less, more preferably 2% by mass or less, even more preferably 1% by mass or less, particularly preferably 0.6% by mass or less.

[0199] The thermoplastic resin composition of this disclosure may contain components other than the processing aid, the masterbatch, and the thermoplastic resin (D). Other components besides the processing aid, the masterbatch, and the thermoplastic resin (D) mentioned above include, for example, anti-sticking agents; ultraviolet absorbers; flame retardants; reinforcing materials such as glass fibers and glass powder; stabilizers such as minerals and flakes; lubricants such as silicone oil and molybdenum disulfide; pigments such as titanium dioxide and red iron oxide; conductive agents such as carbon black; impact-resistant agents such as rubber; antioxidants such as hindered phenols and phosphorus; nucleating agents and antiblocking agents such as metal salts and sorbitol acetals; and the lubricant (A) mentioned above.

[0200] The thermoplastic resin composition of this disclosure may be obtained, for example, by preparing a masterbatch of this disclosure in advance and putting it into a mixer or the like with the thermoplastic resin (D) and performing a mixing step, and then discharging the mixture from the mixer or the like; or by putting the thermoplastic resin (D), the lubricant (A), the resin (B), and optionally the thermoplastic resin (C) into a mixer or the like and performing a mixing step, and then discharging the mixture from the mixer or the like. This disclosure also provides a method for producing the above-described thermoplastic resin composition, including a mixing step and a discharging step.

[0201] In the method for producing the thermoplastic resin composition of this disclosure, a molding step may be performed after the extrusion step in which the extruded material is molded using a molding machine or the like.

[0202] The mixing step, dispensing step, and molding step in the method for producing the thermoplastic resin composition of this disclosure are the same as those described in the method for producing the processing aid of this disclosure.

[0203] <Molded body> The molded articles of this disclosure are made using the thermoplastic resin composition of this disclosure, and may be obtained, for example, by a molding process that molds the thermoplastic resin composition of this disclosure. This disclosure also relates to a method for manufacturing the molded article of this disclosure, including a molding process. The thermoplastic resin compositions of this disclosure are suitable for molded articles in the form of tubes, films, or sheets, but can also be applied to molded articles of other shapes.

[0204] The molding process described above is the same as that described in the method for manufacturing the processing aid of this disclosure.

[0205] In the above molding process, the molding temperature (extrusion temperature) during molding is generally set at a temperature that is equal to or higher than the melting point of the above thermoplastic resin (D), lower than the decomposition temperature of the above lubricant (A), and lower than the decomposition temperature of the above resin (B). When components other than the lubricant (A) and the resin (B) are included, it is preferable to set the molding temperature in consideration of those components. In terms of the remarkable exertion of the effect of the above processing aid, it is preferably in the range of 160°C or higher and 270°C or lower. In the case of extrusion molding, the above molding temperature may also be referred to as the extrusion temperature.

[0206] The use of the molded body of the present disclosure is not particularly limited. For example, it includes bags, coating materials, tableware such as beverage containers, electric wires, cables, pipes, fibers, bottles, gasoline tanks, and other various industrial molded products.

[0207] Although the embodiments have been described above, it will be understood that various changes in form and details are possible without departing from the spirit and scope of the claims.

Examples

[0208] Next, the present disclosure will be described with reference to examples, but the present disclosure is not limited to such examples only.

[0209] In the examples and comparative examples, the following materials were used. (Lubricant (A)) Polysorbate60: Polysorbate 60 (MFR: >500 g / 10 min) Zn-St: Zinc stearate (MFR: >500 g / 10 min) Mg-C18(OH): Magnesium 12-hydroxystearate (MFR: >500 g / 10 min) PE-wax #1: General polymerization type polyethylene wax (acid value: 0 mgKOH / g, melting point: 122°C, melt viscosity (140°C): 80 mPa·s, MFR: >500 g / 10 min) PE-wax #2: Metallocene-catalyzed polyethylene wax (acid value: 0 mgKOH / g, melting point: 100 °C, melt viscosity (140 °C): 300 mPa·s, MFR: >500 g / 10 min) PE-wax #3: Acid-modified type polyethylene wax (acid value: 17 mgKOH / g, melting point: 107 °C, melt viscosity (140 °C): 300 mPa·s, MFR: >500 g / 10 min) PE-wax #4: Oxidized type (high acid value) polyethylene wax (acid value: 30 mgKOH / g, melting point: 102 °C, melt viscosity (140 °C): 265 mPa·s, MFR: >500 g / 10 min) (Resin (B1)) EVOH: Ethylene-vinyl alcohol copolymer (ethylene content: 38 mol%, MFR: 1.6 g / 10 min, melting point: 172 °C) PLA: Polylactic acid (MFR: 3 g / 10 min, melting point: 153 °C) PBS: Polybutylene succinate (MFR: 22 g / 10 min, melting point: 114 °C) (Resin (B2)) PLA: Polylactic acid (MFR: 3 g / 10 min, melting point: 153 °C) PBS: Polybutylene succinate (MFR: 22 g / 10 min, melting point: 11 cuatro °C) (Matrix resin, carrier resin) m-LLDPE-1: Metallocene-catalyzed linear low-density polyethylene (MFR: 0.7 g / 10 min, melting point: 123 °C, d = 0.926, MIR = 28.1) m-LLDPE-2: Metallocene-catalyzed linear low-density polyethylene (MFR: 2.0 g / 10 min, melting point: 121 °C, d = 0.925, MIR = 23.6) ZN-LLDPE-1: Ziegler-Natta-catalyzed linear low-density polyethylene (MFR: 0.8 g / 10 min, melting point: 123 °C, d = 0.925, MIR = 27.0) ZN-LLDPE-2: Ziegler-Natta-catalyzed linear low-density polyethylene (MFR: 2.0 g / 10 min, melting point: 121 °C, d = 0.918, MIR = 23.2) (Other additives (E) (Synergist)) It should be noted that in the translation of "11 cuatro °C" in item , it seems there is an error in the original text. It should probably be "114 °C", and this is translated accordingly.PCL: Polycaprolactone (Mw: 80,000, Melting point: 55℃) PEG-1: Polyethylene glycol (Mn: 8,000, Melting point: 63°C) MB50-002: Silicone (Masterbatch containing ultra-high molecular weight silicone, manufactured by Dupont) GENIOPLAST PELLET S: Silicone (Ultra-high molecular weight silicone, manufactured by Asahi Kasei Wacker) Pebax MV1072: Polyamide-polyether block copolymer (manufactured by Arkema)

[0210] Comparative Examples 1-5, Examples 1-87 First, the matrix resin (thermoplastic resin (D)), lubricant (A), resin (B1), and resin (B2) were melt-mixed in the proportions shown in Table 1 using a twin-screw extruder (TEX25αIII, manufactured by Japan Steel Works) under the conditions of a cylinder temperature of 180-200°C, a die temperature of 200°C, and a screw rotation speed of 400 rpm to obtain a compound. Next, the processability of the obtained compound was evaluated by the extrusion evaluation described below. The results are shown in Table 1. Note that since the lubricant (A), resin (B1), and resin (B2) used do not contain fluorine, the fluorine content in the processing aid was 0% by mass.

[0211] Examples 88-90 First, carrier resin (thermoplastic resin (C)), lubricant (A), resin (B1), and resin (B2) were melt-kneaded in the proportions shown in Table 2 using a twin-screw extruder (TEX25αIII, manufactured by Japan Steel Works) at a cylinder temperature of 180-200°C, a die temperature of 200°C, and a screw rotation speed of 400 rpm, so that the concentrations of lubricant (A), resin (B1), and resin (B2) were 25% by mass, to obtain a masterbatch (MB). Next, the processability of the obtained masterbatch after dry blending with matrix resin in the proportions shown in Table 2 was evaluated by the extrusion evaluation described below. The results are shown in Table 2. Note that since none of the lubricant (A), resin (B1), and resin (B2) used contained fluorine, the fluorine content in the processing aids was 0% by mass.

[0212] Examples 91-95 First, the matrix resin (thermoplastic resin (D)), lubricant (A), resin (B1), resin (B2), and other additives (E) were melt-mixed using a twin-screw extruder (TEX25αIII, manufactured by Japan Steel Works) at a cylinder temperature of 180-200°C, a die temperature of 200°C, and a screw rotation speed of 400 rpm to obtain a compound. Next, the processability of the obtained compound was evaluated by the extrusion evaluation described below. The results are shown in Table 3. Note that since the lubricant (A), resin (B1), and resin (B2) used do not contain fluorine, the fluorine content in the processing aids was 0% by mass.

[0213] <Extrusion Evaluation> Each material was extruded for 60 minutes using a single-screw extruder (HAAKE Rheomex OS, L / D: 33, screw diameter: 20 mm, die diameter: 2 mm) under the following conditions: cylinder temperature 170-200°C, die temperature 200°C, and shear rate 450 / second. The following items were evaluated. Prior to each test run, 15% by mass of silica-containing linear low-density polyethylene was placed in the hopper, the screw rotation speed was increased to 150 rpm, and purging was performed for approximately 15 minutes. Next, the same matrix resin to be used in the test was placed in, and purging was performed for approximately 15 minutes. After that, the screw rotation speed was returned to 30 rpm and extrusion was performed until the temperature stabilized. After confirming that the initial pressure had returned, the next experiment was conducted. If the initial pressure had not returned, the above purging procedure was repeated until the initial pressure returned before the next experiment was conducted. (Melt Fracture (MF) state) Extrusion was performed using only the matrix resin until melt fracture occurred across the entire surface and the pressure stabilized. The point at which the screw became visible was defined as zero, and extrusion was continued for 60 minutes. In cases where processing aids or masterbatches were used, these were added to the hopper at the zero point. The appearance of the strands at the beginning and end of extrusion was then visually and tactilely inspected, and the change in MF observed at the beginning of extrusion was evaluated according to the following criteria. A smaller value indicates better performance. Disappearance: MF completely disappeared Does not disappear: MF is the same as in the case of only the matrix resin, or MF decreases but does not disappear completely (Die Build-up (DBU)) For the samples in which MF completely disappeared, extrusion evaluation was performed by long-run molding (3 hours), the state of the die after extrusion was visually confirmed, and the presence or absence of DBU (die coking) was evaluated Evaluation was performed in 5 grades from 1 to 5. The smaller the value, the less the amount of DBU generated and the better. 1 indicates that no DBU occurred (Storage stability test) Regarding Example 5, Example 12, Example 17, Example 22, Example 30, Example 31, and Example 81, strand samples were collected after long-run molding (3 hours) and allowed to stand at 80°C for 24 hours. After 24 hours, a sensory evaluation (tactile sensation) was performed on the slipperiness of the strand surface, and the slipperiness before and after the test was evaluated according to the following criteria (presence or absence of bleed-out). The results are shown in Table 1 Yes: The slipperiness after the test is higher than before the test No: No change before and after the test

[0214] [Table 1]

[0215] [[ID=^25]] [Table 2]

[0216] [[ID=3^4]] [Table 3] ...

[0217] From the results of the examples, it is presumed that the effects of the invention of the present application were obtained by the following mechanism Since the molten resin (B) has a functional group, the interaction with the metal on the inner surface of the extruder is promoted, and the resin (B) adheres to the metal surface on the inner surface of the extruder to form a coating layer, thereby improving the fluidity of the matrix resin (LLDPE) Furthermore, it is believed that a synergistic effect was achieved by using resin (B) and lubricant (A) in combination, resulting in a significant improvement in processability.

Claims

1. It comprises a lubricant (A) and a resin (B), The resin (B) includes a structural unit represented by the following formula 1, An extrusion molding processing aid wherein the lubricant (A) is at least one selected from the group consisting of polysorbate, zinc stearate, magnesium 12-hydroxystearate, and polyethylene wax. -X-(CR １ R ２ ) ｎ -Y-(CR ３ R ４ ) ｍ -Z- (Formula 1) (In formula 1, X is a single bond or a divalent group composed of at least one selected from the group consisting of X1 and X2, X1 is a group composed of at least one selected from the group consisting of -C(=O)-, -CR'R'-, and -C(OR')R'- (wherein R' is independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms in each occurrence). X2 is an aromatic hydrocarbon group having 1 to 12 carbon atoms, which may have substituents. Y and Z are each independently composed of at least one group selected from the group consisting of a single bond, -O-, -C(=O)-, -C(=O)O-, and -C(OR')R'- (wherein R' is independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms in each occurrence). R １ 、 R ２ 、 R ３ and R ４ are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, n and m are each independent integers between 0 and 10. At least one of X, Y, and Z is -C(=O)-, -C(=O)O-, or -C(OR')R'-.

2. The extrusion processing aid according to claim 1, which is substantially free of fluorine.

3. The extrusion processing aid according to claim 1 or 2, wherein the lubricant (A) is at least one selected from the group consisting of waxes, alcohols, and surfactants.

4. The extrusion processing aid according to claim 1 or 2, wherein the lubricant (A) is at least one selected from the group consisting of sugar-type surfactants, metal soaps, and polyethylene waxes.

5. The extrusion processing aid according to claim 1 or 2, wherein X in formula 1 is a divalent group comprising at least one selected from the group consisting of -C(=O)-, -CR'R'-, and -C(OR')R'- (wherein R' is independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms in each occurrence).

6. The extrusion processing aid according to claim 1 or 2, wherein Y and Z in formula 1 are each independently composed of at least one group selected from the group consisting of a single bond, -O-, -C(=O)-, and -C(=O)O-.

7. The extrusion molding processing aid according to claim 1 or 2, wherein the melting point of the resin (B) is 65°C or higher.

8. The extrusion processing aid according to claim 1 or 2, wherein the resin (B) is at least one selected from the group consisting of polylactic acid, polybutylene succinate, ethylene-vinyl alcohol copolymer, and polybutylene succinate adipate.

9. The extrusion processing aid according to claim 1 or 2, wherein the resin (B) is at least one selected from the group consisting of polylactic acid, polybutylene succinate, and ethylene-vinyl alcohol copolymer.

10. A masterbatch comprising the extrusion processing aid described in claim 1 and a thermoplastic resin (C).

11. The masterbatch according to claim 10, wherein the thermoplastic resin (C) is a polyolefin resin.

12. The thermoplastic resin (C) is at least one selected from the group consisting of metallocene-catalyzed linear low-density polyethylene and Ziegler-Natta-catalyzed linear low-density polyethylene. The masterbatch according to claim 10, wherein the mass ratio of the thermoplastic resin (C) and the processing aid (thermoplastic resin (C): processing aid for extrusion molding) is 92:8 to 70:

30.

13. A thermoplastic resin composition comprising an extrusion processing aid according to claim 1 or 2, and / or a masterbatch according to claim 10 or 11, and a thermoplastic resin (D).

14. The thermoplastic resin composition according to claim 13, wherein the thermoplastic resin (D) is a polyolefin resin.

15. The thermoplastic resin (D) is at least one selected from the group consisting of metallocene-catalyzed linear low-density polyethylene and Ziegler-Natta-catalyzed linear low-density polyethylene. The thermoplastic resin composition according to claim 14, wherein the content of the extrusion processing aid is 0.02 to 3% by mass.

16. A molded article using the thermoplastic resin composition according to claim 13.

17. The molded article according to claim 16, which is tubular, film-like, or sheet-like.

18. A method for producing an extrusion molding aid according to claim 1 or 2, comprising a mixing step and a dispensing step.

19. A method for producing a masterbatch according to claim 10 or 11, comprising a mixing step and a dispensing step.

20. A method for producing a thermoplastic resin composition according to claim 13, comprising a mixing step and a dispensing step.

21. A method for manufacturing a molded article according to claim 16, including a molding step.

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